JPS6049894B2 - photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material (hereinafter referred to as a "photosensitive material"), and particularly to a photosensitive material that is antistatic.

Photosensitive materials generally consist of a photosensitive photographic emulsion layer (hereinafter referred to as "photosensitive layer") on an insulating plastic film support.
, an antihalation layer, a protective layer, an intermediate layer, an undercoat layer, and a backing layer (hereinafter referred to as "back layer").

In recent years, manufacturing technology for photosensitive materials has significantly improved, and for example, the coating speed of each layer and the cutting/cutting speed have been significantly increased. Similarly, the speed of handling photosensitive materials during photography,
The transport speed of the photosensitive material in the development process has also been significantly increased.

For this reason, during the production or use of photosensitive materials, it has become easier for photosensitive materials to become charged due to contact friction or peeling between other objects or between photosensitive materials.

As is well known, the photosensitive material not only attracts charged dust and the like and causes various malfunctions, but also, in severe cases, causes spark discharge, causing so-called static marks, which can lead to fatal malfunctions.

Conventionally, polymer electrolytes or surfactants have often been used as antistatic agents for back layers.

The antistatic performance of these polymer electrolytes or surfactants is highly dependent on humidity; at high humidity, they are conductive enough to achieve the initial purpose, but at low humidity, the conductivity decreases markedly. Also, if it is left in high humidity, it will absorb moisture, and if it is overlapped with a photosensitive layer, the back surface and the surface of the photosensitive layer will stick together, causing a failure called adhesion failure.Also, in general, polymer electrolytes and low molecular surfactants Because they are water-soluble, these antistatic layers may dissolve into the processing solution during development and combine with other substances present in the processing solution, creating turbidity or sludge, or may adsorb other substances to the backing layer. In order to solve the problem of adhesion failure, methods using colloids of amorphous inorganic oxides have been used, but colloidal sols of these inorganic oxides do not have antistatic properties after development. In these cases, the humidity dependence of antistatic properties has not been sufficiently resolved.

Although there is a method in which a carbon black fraction layer is provided for both antihalation and antistatic properties, this carbon black layer is removed during the development process, and the antistatic properties are lost after processing.

The first object of the present invention is to provide a photosensitive material that has excellent antistatic properties.

A second object of the present invention is to provide a photosensitive material that has antistatic properties that are not dependent on humidity. A third object of the present invention is to provide a photosensitive material provided with an antistatic layer that does not adhere to other adjoining surfaces even in high humidity. A fourth object of the present invention is to provide a photosensitive material having an antistatic layer in which the antistatic agent does not elute into the processing solution during development and does not cause turbidity or sludge due to elution. A fifth object of the present invention is to provide a photosensitive material having an antistatic layer that does not exhibit any deterioration in antistatic performance during development. These objects of the present invention provide a photosensitive material comprising at least one photosensitive layer on one side of a plastic film support and an antistatic layer on the other side, the antistatic layer comprising ZnO, TiO2, SnO2, A
e2O3, In2O3, SlO2, MgO, BaO, M
At least one crystalline metal oxide or composite oxide thereof selected from OO3, whose volume resistivity is 107Ω
- Achieved by a photographic material characterized by containing 0.1 to 3.0 y per square meter of fine particles having a particle size of 0.5 μm or less and having a particle size of 0.5 μm or less.

Crystalline oxide or composite thereof used in the present invention. The oxide fine particles have a volume resistivity of 10 7 Ω·1 or less, more preferably 1 CF'Ωα or less. Further, the particle size is preferably 0.01 to 0.5μ, particularly 0.02 to 0.5μ. The method for producing fine particles of conductive crystalline metal oxides or composite oxides used in the present invention is described in detail in Japanese Patent Application No. 55-47663, but mainly as follows. Manufactured by a method.

The first method is to prepare metal oxide fine particles by firing, and then heat-treat the metal oxide particles in the presence of a different type of atom to improve conductivity.The second method is to prepare metal oxide fine particles by firing and heat-treating the metal oxide fine particles in the presence of a different type of atom to improve conductivity. There are two methods: a method in which atoms coexist, and a third method in which oxygen defects are introduced by lowering the oxygen concentration in the atmosphere when producing metal fine particles by firing. Examples containing different atoms include Ae, In, etc. for Zr)o, T
Nb, Ta, etc. for iO2, S for SnO2
b, Nbl, complete halogen, etc.

The amount of foreign atoms added is preferably in the range of 0.01 to 30 rT101%, particularly preferably 0.1 to 10 n101%.The amount of conductive particles used is 0.05 y/d to 3
f/a is good, and 0.05 f/b to 2y/d is particularly preferable. The fine particle binder used in forming the conductive layer of the present invention includes cellulose esters such as cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride,
Homopolymers or semipolymers containing vinyl chloride, styrene, acrylonitrile, vinyl acetate, alkyl (alkyl group C1-C4) acrylate, vinylpyrrolidone, etc.
Examples include soluble polyester, polycarbonate, and soluble polyamide. For dispersion, a dispersion liquid such as a titanium or silane dispersant may be added. Further, there is no problem in adding a binder crosslinking agent or the like. As a titanium-based dispersant, US Patent No. 4069
Titanate coupling agents described in No. 192, No. 4080353, etc., and PreneAct (trade name:
(manufactured by Ajinomoto Co., Inc.).

Examples of known silane-based dispersants include vinyltrikuyama resilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacrylooxypropyltrimethoxysilane. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a silane coupling agent. Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, isothiocyanate crosslinking agents, aziridine crosslinking agents, and epoxy crosslinking agents.

The conductivity of the present invention may be achieved by dispersing conductive fine particles in a binder and providing the support layer, or by subjecting the support to a subbing treatment and depositing the conductive fine particles thereon.

Examples of the support used in the present invention include cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene or polypropylene coated paper.

In the present invention, it is preferable to further provide a hydrophobic polymer layer on the conductive layer. In the present invention, the hydrophobic polymer layer provided on the conductive layer may be applied in the form of a solution dissolved in an organic solvent or an aqueous latex, and the coating amount is preferably about 0.05y/d to 1y/Rfl in terms of dry weight. . Examples of the hydrophobic polymer include vinyl polymers including cellulose esters (eg, nitrocellulose, cellulose acetate), vinyl chloride, vinylidene chloride, vinyl acrylate, and polymers such as organic solvent-soluble polyamides and polyesters. This layer is coated with a slippery agent to impart slippery properties, for example,
There is no problem in using organic carboxylic acid amides such as those described in No. 79435, and there is no problem in adding a matting agent or the like.

The conductive layer and the hydrophobic polymer layer can be coated by conventional methods such as roller coating, air knife coating, gravure coating, percoat, and curtain coating.

The photosensitive material of the present invention has at least one photosensitive layer on the photosensitive layer side of the support, and if necessary, an undercoat layer, an antihalation layer, an intermediate layer, and a surface protective layer. Become.

As the undercoat layer used in the present invention, JP-A-51-1355
No. 26, U.S. Patent No. 3143421, U.S. Patent No. 358650
No. 8, No. 2698235, No. 356745? Vinylidene chloride copolymer as described in the specification etc.
JP-A No. 51-1141, U.S. Patent No. 3615556
diolefin-based copolymers such as butadiene as described in JP-A No. 51-584, copolymers containing glycidiacrylate or glycidyl methacrylate as described in JP-A No. 51-584, etc.; 1977-
Polyamide epichlorohydrin resin as described in 24923 specification etc., JP-A-50-139536
Maleic anhydride-containing copolymers such as those described in can be used. The photosensitive layer is preferably a silver halide emulsion layer.

Examples of the silver halide include silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Various additives used in photographic emulsions, such as chemical sensitizers, antifoggants, surfactants, protective colloids, hardeners, polymer latex,
There are no particular limitations on color couplers, matting agents, sensitizing dyes, etc., and for example, the descriptions in Research Disclosure, 17, pages 22-28 (December 197) may be referred to. Further, there are no particular restrictions on the intermediate layer, antihalation layer, surface protective layer, etc., and the above-mentioned resin. Various additives described in H. Disclosure Magazine can be used.

There are no particular restrictions on the method for producing the photographic emulsion or the method for coating the various photographic layers on the support, and the descriptions in the above-mentioned journal of Resarte Disclosure can be referred to. Examples of the light-sensitive material of the present invention include color negative film, color reversal film, and black and white photographic film.

The present invention will be further explained below with reference to Examples.

Example 1 65 parts by weight of stannic chloride hydrate and 1.0 parts by weight of antimony trichloride.
5 parts by weight were dissolved in 100 parts by volume of ethanol to obtain a homogeneous solution.

Add a 1N aqueous sodium hydroxide solution to this solution.
The solution was added dropwise until the H content reached 3 to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was heated to 50°C.
After standing for 24 hours, a reddish brown colloidal precipitate was obtained. A reddish-brown colloidal precipitate was separated by centrifugation.

In order to remove excess ions, water was added to the precipitate and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. 100 parts by weight of the colloidal precipitate from which excess ions had been removed were remixed with 1000 parts by weight of water and sprayed into a calcining furnace heated to 650° C. to obtain fine particles with an average particle size of 0.15 μm and a bluish tinge.

The above conductive fine particles were dispersed for 5 hours using a paint shaker (Toyo Seiza Seisakusho) according to the following formulation.

The above conductive fine particles 20 parts Saran*
10〃Methyl ethyl ketone
150 * Vinylidene chloride copolymer, trade name of Asahi Tau Co., Ltd. (Saran F-310) Using this dispersion, prepare a coating solution with the following formulation, and apply the dry film coating amount to a 100μ thick polyethylene terephthalate film. is 1.3y/d
It was applied and dried at 130°C for 2 minutes.

The above dispersion 15 parts by weight Saran
3. Methyl ethyl ketone
100〃Cyclohexanone 2
0〃m-cresol 5〃Furthermore, on this layer, apply the following liquid with a dry film coating amount of 0.2y/Rll.
It was applied and dried at 30°C for 1 minute.

Cellulose triacetate 1 part by weight Methylene dichloride 60 Ethylene dichloride
40 Erucic acid amide 0.01 This coated surface was used as a back layer, and a micro silver halide emulsion was coated on the opposite surface via an undercoat layer.

The surface resistance value of the back layer was measured using an insulation resistance measuring device (VE-me type manufactured by Kawaguchi Electric Co., Ltd.) at 25°C and 125%RH.
It was 1Cf3Ω. Also, bring the back side and the photographic emulsifier side into contact and apply a load of 2k9/10cI to 50'C.
Although it was left for one period at 180% RH, no adhesion occurred.

Example 2 A dispersion of conductive fine particles was prepared in the same manner as in Example 1, and this dispersion was used to prepare a coating solution with the following formulation. It was coated in the same manner as A and dried at 120'C for 3 minutes.

Dispersion liquid 15 parts by weight Saran
3〃r! 4EK70〃 Methanol 30〃Cyclohexanone 20〃Furthermore, apply the following liquid on top of this layer so that the dry film coating amount is 0.3y/d.1
It was dried at 20°C for 2 minutes.

Cellulose diacetate 10 parts by weight acetone
240 Methanol
480 Silicon dioxide 0.1 (average particle size 1 μm) A sample was prepared as a comparative sample by the method described in Example 2 of JP-A-55-7763.

A solution with the following formulation was applied and dried.

2C1θ (Toni 5) 8 parts by weight FI2Cl parts Methanol 500 Acetone
300 Further, on this layer, a dispersion of cellulose diacetate and silicon dioxide fine particles using a mixed solution of 300 ml of acetone and 600 ml of methanol was applied.

The surface resistance of the obtained film was measured at 25° C. and 25% RH, and the results were as follows. The surface resistance of the sample coated with fine particles of tin antimony oxide composite oxide remained almost unchanged before and after development.

Example 3 The conductive fine particles of Example 1 were dispersed in the following formulation using a paint shaker for 3 hours.

Conductive fine particles 20 parts Cellulose diacetate 5 Acetone
150 Using this dispersion, a coating solution with the following formulation was prepared and coated onto a cellulose triacetate film with a thickness of 135 μm so that the dry film coating amount was 1.5 f/TTI, and dried.

Dispersion 7 parts by weight Cellulose diacetate 1 Acetone
70 Methanol 3
0. On top of this layer, apply the following liquid with a dry film coating amount of 0.2y.
/d and dried.

Cellulose diacetate 1.5 parts by weight Acetone 30 Methanol
70 A subbing layer was provided on the opposite side of this coated surface, and a silver halide color emulsion was coated thereon to prepare a light-sensitive photographic film.

The back layer of the obtained film was rubbed vigorously with a nylon roller at 25° C. and 25% RH, but no static marks were observed.

Claims (1)

[Claims] 1. In a photographic material comprising at least one light-sensitive silver halide photographic emulsion layer on one side of a plastic film support and an antistatic layer on the other side, the antistatic layer is ZnO, TiO_2, SnO_2, Al_2O
_3, In_2O_3, SiO_2, MgO, BaO,
Fine particles of at least one crystalline metal oxide selected from MoO_3 or composite oxides thereof with a volume resistivity of 10_7 Ω・cm or less and a particle size of 0.5 μm or less per 1 square meter. A silver halide photographic material containing 3.0g.